Quaternary ammonium salts



methyl-sulfate, methyl- Patented Dec. 30, 1952 UNITED STATES PATENT I OFFICE r. to General York, N. Y.,

No Drawing.

Aniline & Film Corporation, New

a corporation of Delaware Application January 10, 1950,

Serial No. 137,883

3 Claims.

R wherein A represents a dehydroabietinyl radical:

CH CH2- CH(CH3)2 X represents an anion of a salt-forming acid, and the Rs represent N-substituents of the class consisting of lower alkyl (e. g. of 1 to 4 carbon atoms), p-hydroxyethyl, and polyethylene ether radicals, including at least 2 and especially 2 to oxyethylene radicals. The compositions of the invention may be single compounds, but are usually mixtures of compounds of the foregoing general formula. 7 v

The compositions of this invention are watersoluble and characterized by outstanding emulsiiying power for water-insoluble hydrocarbons. More particularly, compounds containing 2 to 5 oxyethylene radicals per molecule yield stable aqueous emulsions of aliphatic water-immiscible solvents, while those containing more than 5 oxyethylene radicals per molecule yield stable aqueous emulsions of aromatic water-immiscible solvents. The products also possess detergent properties in aqueous solution.

The quaternary ammonium salts of the invention can be prepared in a number of ways. Thus, N-polyethenoxy derivatives of dehydroabietinyl amine, prepared by condensation of 2 to 40 mols of ethylene oxide with dehydroabietinyl primary amine can be converted to quaternary ammonium salts by reaction with alkylating agents such as alkyl esters of inorganic acids, e. g. diethylor dior ethyl-iodide, or dibutyl-suliate, suitable for the alkylation of amines. A mixture is thus obtained of quaternary ammonium salts in which the N-substituents 'hydroabietinyl amine (e.

2 represented by R. are the alkyl groups of the alkylating agent, and the hydroxyethyl or polyethylene glycol radicals originally introduced'by condensation with ethylene oxide. Condensation products of this type containing 4 to 40 ethenoxy radicals in the substituent groups of pentavalent nitrogen are disclosed in my copending application Serial No. 133,223, filed December 15, 1949.

Another methodfor preparingconipositions of this invention involves N-alkylation of dehydroabietinyl primary amine by reaction with an alkylating agent such as dimethyl-, diethyl- .or dibutyl-sulfate, or methylor ethyl-iodide, insuch proportions as to form a tertiary amine, followed by condensation of the tertiary amine with 2 to 40 mols of ethylene oxide, for example, in accordance with the process of USP 2,127,476. The resulting quaternary ammonium bases can be readily converted to salts 'by neutralizing .them with a salt-forming acid.

The following examples, wherein parts are by weight, illustrate the preparation of a numberof quaternary ammonium salt compositions in accordance with my invention.

Example 1 150.5 parts of a condensation product of deg. a commercial product known as Rosin Amine D) with about ,9 mols of ethylene oxide (prepared, for example, as described in my copending application Serial No. 133,223, by condensation of 59 parts of dehydroabietinyl amine with 101.7 parts of ethylene oxide in the presence of sodium methylate as a catalyst at to C.) are agitated, and'23.8 parts of dimethyl sulfate are slowly added while raising the temperature .to 80 C. The reaction mixture is maintained at this temperature for 6;hours and then cooled. The resulting quaternary dehydroabietinyl methyl polyethenoxylated ammonium sulfate is a semi-solid amorphous mass, soluble. in water.

When tested for detergency in water at concentrations from 0.05 to 0.5 for washing soiled cotton cloth having a reflecting power of 52%, the reflecting power of the cloth was increased to 62 to 65%, whereas the original dehydroabietinyi amine in the form of its acetate, at similar concentrations, increased the reflecting power of the same cloth to at most 54% under similar testing conditions. The detergency of the product was found to be of the same order as that of a commercially known alkylphenol polyethylene oxide condensation product noted for its excellence as a detergent. Stable aqueous emulsions of ben- .3. zene, toluene or xylene are readily formed by incorporating a small proportion of the quaternary Ewampl 2 103 parts a; "a condensation-product of dehydroabietinyl amine with about half the amount oi ethylene oxide employed in preparing the starting 'material of 23.3 parts of dimethyl sulfate by the procedure employed in the foregoing example. A product of similar appearance is obtainedwhich yields stable emulsions of petroleum distillates siich as kerosene, when incorporated together withsuch solvents in water. The quaternary ammonium salt thus obtained contains between 4 and 5 oxyethylene radicals per molecule of quaternary ammonium compound.

Example 3 1 part of dehydroabietinyl diethylamine, prepared by reaction of dehydroabietinyl primary amine with the, calculated amount of ethyliodide,'and liberation of the free-amine from the sesse's properti'essimilar to "those of the product of Example v1. 7

Instead or dimethyl-sulfate, diethylor dib'utyl-sulfate can be used in equivalent proportions in the foregoing examples to produce corresponding quaternary a'mmonium salts having ethyl or 'butyl groups attached tog-nitrogen. Salts of other acids can. be I prepared 'from the sulfate or iodide initially obtained, "by conversion of the salt to the free base (e. g. "by reaction of the sulfate with barium hydroxide or the iodide with silver oxide) and neutralizing the quaternary "ammonium base thusob'tained with another acid such as hydrochloric, *hydrobromic, phosphoric, acetic, 'formicah'd the like. If the free base is "originally obtained as in Example 3, it can be neutralizeddirectlywith an acid of the aforesaid class.

"Condensation products "containing larger proportionsof'ethylene*oxidefeig. up to 40 mols of ethylene oxide per mol of amine, obtained, for exampleasdisclosed'in the examples of my copending application Serial No. 133,223, can be convertedto quaternary ammonium salts of this invention inaccordance'with the procedures of Example 1 is reacted with Suflicient 10% sulfuric acid 0 Examples 1 and 2, and similar condensation products containing as little as 2 mols of ethylene oxide per mol of amine can be similarly converted to quaternary ammonium salts. In condensing dehydroabietinyl dialkylamines with ethylene oxide as disclosed in Example 3, the protain quaternary erties.

Variations and modifications which will be obvious to those skilled in the art can be made in the foregoing-procedures without departing from the scope ornature of the invention.

I claim:

1 U A salt of a quaternary ammonium base having the formula:

wherein Xr'epres'e'nts 'th'e'aiiion of a salt-formin'g acid, A repres'e'nt's'a dehydro'abietin'yl'radical, and the Rs represent N -'substitue'n'ts of the'class fl-hydroxyethyl and polyethylene ether radicals. 2. Aquatern'ary ammonium salt as defined in claim 1, containing 2 to 40 oxyethylene radicals per molecule.

3. N -methylated-N -polyetho'xylated dehydroabietinyl ammonium sulfate containing about 9 oxyethylene radicals per molecule.

HERBERT L. SANDERS.

REFERENCES CITED The following references are of record in the file of this patent:

OTHER REFERENCES Borglin: Soap and Sanitary Chemistry, December l947,-pp. 147, 149 and 167. 

1. A SALT OF A QUATERNARY AMMONIUM BASE HAVING THE FORMULA: 